JP2846068B2 - Paint formulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint compounding liquid used for surface finishing of leathers such as PVC leather, synthetic leather, artificial leather, natural leather, and the like, or surface finishing of molded resin, metal, woodwork, etc. The present invention relates to a coating composition liquid used in the case of, particularly, a coating composition liquid that provides a touch feeling rich in natural skin, has functionality such as moisture permeability, and provides a coating film with excellent mechanical strength. It is about.

[Prior art] Conventionally, many paints have been used as finishing paints for leathers, synthetic resin molded products, metal molded products, woodwork products, etc.
In particular, synthetic resin paints are functionally selected and used depending on the intended use. However, when a person directly touches the skin,
In the field of contact and use, when the skin comes into contact with the skin, there is no uncomfortable feeling, no stickiness due to sweat, and high moisture permeability, high moisture absorption, high moisture release paint film. Is desired. As an example of this, a leather powder dispersed in a synthetic resin paint such as polyurethane or vinyl chloride has been proposed. Also, if the content of the leather powder is too large, the surface feel is good but the strength is small, and there are disadvantages such as the leather powder falling off from the coating film when rubbing, and it is not satisfactory. Absent. The inventor of the present invention has completed the present invention as a result of intensive studies on paints that can provide a coating film that does not feel uncomfortable with human skin that is not satisfied by these conventional methods.

[Structure and Effect of the Invention] That is, the present invention is a coating composition liquid comprising a dispersion liquid in which particles made of natural collagen are dispersed in an organic solvent solution of a synthetic resin mainly composed of a polyamino acid urethane resin. In the present invention, the polyamino acid urethane is a copolymer of a polyurethane and a polyamino acid, and a conventionally known polyamino acid urethane can be used. As a general method for producing a polyamino acid urethane, there is a method in which an N-carboxy-α-amino acid anhydride is addition-polymerized to a polyurethane. As the polyurethane used here, all conventionally known polyurethanes can be used. For example, organic diisocyanates and long-chain diols,
And a polyurethane obtained by a reaction with a chain extender.Typical examples of the organic diisocyanate include an alicyclic organic diisocyanate, an aliphatic organic diisocyanate, and an aromatic organic diisocyanate. Diols, polyether diols, polyamide ester diols, polycarbonate diols, etc. can be used. As the chain extender, compounds containing two active hydrogens such as low molecular weight glycol, low molecular weight diamine, low molecular weight amino alcohol are used. It is possible to use a polyurethane made of a mixture thereof. Depending on the application, these materials should be selected.For example, in applications where hydrolysis resistance is required and discoloration resistance is required, as the organic diisocyanate,
An alicyclic diisocyanate or an aliphatic diisocyanate may be used, and a polycarbonate diol or a polyether diol may be used as the long-chain diol.

Examples of the N-carboxy-α-amino acid anhydride to be subjected to the addition reaction to the polyurethane include an anhydride of γ-methyl-L-glutamate and an anhydride of a carboxylic acid at the γ-position such as ethyl, propyl and butyl ester. Or leucine anhydride. The polyamino acid segment ratio in the polyamino acid urethane obtained by these reactions is 3% by weight to 85% by weight, preferably 10% by weight to 60% by weight. If the polyamino acid segment ratio is less than 3% by weight, the synthetic polyamino acid particles fall off the coating film, or the functional properties such as moisture permeability cannot be satisfied. It is not preferable because it cannot be performed. On the other hand, if the polyamino acid segment ratio exceeds 85% by weight, the resulting coating film has low elongation, and the mechanical strength against bending, rubbing, etc., is not preferred. The polyamino acid urethane thus obtained is used as an organic solvent solution. Examples of the organic solvent for dissolving the polyamino acid urethane include methylene chloride, chloroform, and chlorinated aliphatic hydrocarbons such as 1,2-dichloroethane, but when the polyurethane segment ratio in the polyamino acid urethane is high, it is difficult to dissolve, Moreover, it is better to avoid as much as possible from the viewpoint of hygiene. Preferred organic solvents include dioxane, N, N-dimethylformamide, N, N-
There are polar organic solvents such as dimethylacetamide, N-methylpyrrolidone, methyl ethyl ketone and tetrahydrofuran. When the organic solvent used is such a polar organic solvent, when the ratio of the amino acid segments of the polyamino acid urethane is 40% or more, it generally tends to become a translucent gel without being dissolved. Therefore, the amino acid segment ratio should be designed in consideration of the type of organic solvent used, the concentration used, and the like. In the present invention, in the organic solvent solution of the polyamino acid urethane thus obtained, in order to modify the properties of the obtained coating film, another synthetic resin or a natural resin is mixed and used. be able to. Also in this case, it is naturally preferable that the polyamino acid segment ratio in the mixed resin is 3% by weight to 85% by weight.

The above-mentioned particles composed of natural collagen dispersed in an organic solvent solution of a synthetic resin mainly composed of a polyamino acid urethane are particles obtained by subjecting animal skin, hair, and the like to various treatments. For example, leather powder crushed at a low temperature, so-called leathers that have been subjected to chrome tanning treatment as those that are currently industrially produced, or
There is particulate collagen which has not been subjected to chrome tanning treatment and is purified by removing extra components other than collagen such as fat by enzymatic decomposition reaction of so-called skin and hair. In the present invention, any of the above can be used, but from the viewpoint of coloring and discoloration of the particles, it is preferable to use the latter particles purified from skin, hair and the like not subjected to chrome tanning.
In other words, the particles pulverized from the leather subjected to the chrome tanning treatment of the former are colored in chrome, so that they cannot be used for light colors such as white, and when used, they are not fat. This is due to the tendency of discoloration due to light or the like due to impurities such as impurities. On the other hand, collagen particles purified by a biochemical reaction treatment that has not been subjected to chrome tanning are colorless (white) particles, so that they can be sufficiently used for white and the like, and because there are no impurities such as fats,
It is preferable because there is almost no discoloration due to light or the like. However, collagen purified in this way by biochemical reaction treatment has been subjected to molecular cross-linking by a chemical reaction because of its high swelling property in water and easy degradation by proteolytic enzymes such as amylase. Is preferred.

The particles made of the natural collagen as described above may be subjected to a treatment such as pulverization in order to make the particles finer in some cases. The smaller the particle size, the larger the particle surface area per unit weight, and the more easily the resulting coating film will have functional properties such as moisture permeability, hygroscopicity, and moisture release, and the coating film will have a smoother surface feel. preferable. The average particle size of the particles is preferably 20 μm or less, more preferably 10 μm
It is as follows. The particles composed of the natural collagen thus obtained are added and dispersed in the above-mentioned organic solvent solution of the polyamino acid urethane to obtain the dispersion coating liquid composition intended for the present invention.

[Effect of the Invention] A coating film of a coating composition obtained from particles composed of a resin composed mainly of polyamino acid urethane and natural collagen obtained as described above is subjected to mechanical force such as bending and kneading. However, because the amino acid urethane polyamino acid segment with high elongation and high mechanical strength has an affinity from the same protein molecular structure as the natural amino acid particles, whitening occurs and particles made of natural collagen fall off. No. Therefore, the amount of the particles composed of natural collagen to the polyamino acid urethane (solid) can be widely selected. Since the amount of polyamino acid segments in the particles consisting of polyamino acid urethane and polyamino acid natural collagen in the total solid content greatly contributes to the surface touch and functional properties of the resulting coating film, it consists of natural collagen By increasing the amount of added particles, a coating film having a large amount of polyamino acid segments and rich in functional properties can be obtained. That is, when particles composed of natural collagen are dispersed in an organic solvent solution of another polymer such as polyurethane without using the polyamino acid urethane, the amount of the particles added is limited in order to prevent the particles from falling off. Since the amount of the polyamino acid segment in the coating film is relatively smaller than that of the present invention, it is difficult to obtain a coating film having the desired functional characteristics of the present invention. Further, the coating film obtained from only the organic solvent solution of polyamino acid urethane, when the polyamino acid segment ratio is large, a coating film rich in functionality intended for the present invention is obtained, but the elongation is small. Since it becomes a coating film, mechanical durability such as bending is inferior, and the object of the present invention cannot be achieved. As described above, the present invention is a coating composition liquid comprising a dispersion liquid for obtaining a functional coating film having a large polyamino acid segment ratio comprising a molecular polyamino acid segment and a particulate polyamino acid segment. The coating film obtained from the compounded liquid is excellent in mechanical strength. The weight of the polyamino acid segment in which the polyamino acid segment in the polyamino acid urethane constituting the liquid mixture of the present invention and the particles made of natural collagen that is the polyamino acid is preferably 20% by weight or more based on the total solid content, More preferably, it is at least 40% by weight. However, these numerical values do not limit the present invention.

In some cases, by adding a coloring agent such as a pigment or a dye to the thus obtained coating composition, the cosmetic properties of the coating film obtained can be enhanced. Also,
An antioxidant, an anti-NOx gas discoloration inhibitor, various deterioration inhibitors and the like can also be added to obtain a good coating film.

The coating composition of the present invention obtained as described above is applied as a finish coating on the surface of leather, synthetic resin molded product, metal molded product, woodwork product and the like. As a coating method, conventionally known methods such as spray coating, gravure coating, knife coating, roll coating, and lamination using release paper can be employed. The concentration may be adjusted so as to obtain an optimum viscosity according to these application methods. In one application. When the coating thickness is insufficient, the coating and drying may be repeated to adjust the coating thickness to a target value. The coating film thus obtained has a surface feel that is comfortable when a person comes into direct contact with the skin, and there is no stickiness due to sweat,
In addition, it has high moisture permeability, high moisture absorption, and high moisture release, and has high strength so that powder does not fall off even when rubbed.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples. In the examples, “parts” and “%” are based on weight, and the characteristic measured values are obtained by the following methods.

(B) Moisture permeability According to the method of JIS L1099 A-1 method, moisture permeability (g / m ²
day).

(B) Moisture absorption Moisture absorption (g / m ² ) when left for 1 hour in an atmosphere at a temperature of 23 ° C and a relative humidity of 30%, and then left for 30 minutes in an atmosphere at a temperature of 23 ° C and a relative humidity of 80%. Expressed by

(C) Humidity release After leaving for 1 hour in an atmosphere at a temperature of 23 ° C. and a relative humidity of 80%, the amount of moisture release after leaving for 30 minutes in an atmosphere of a temperature of 23 ° C. and a relative humidity of 30% (g / m ²⁾ ).

(D) Flex resistance According to the method of JIS K6545 method, it is expressed in 1 to 5 class.

Example 1 (Preparation of Artificial Leather Base) A nonwoven fabric having a weight of 280 g / m ² and a thickness of 1.0 mm was impregnated with a 13% polyurethane-dimethylformamide solution, and an 18% polyurethane-dimethyl After coating the formamide solution with a basis weight of 600 g / m ² , it was immersed and coagulated, washed with water and dried to prepare an artificial leather base.

(Preparation and application of paint liquid mixture-1) Polyamino acid urethane (use of non-yellowing type urethane:
Particles consisting of natural collagen (manufactured by Showa Denko KK) in 100 parts of N, N-dimethylformamide solution (solid content 10%) of LUCKSKIN-UA-3295A (polyamino acid segment 35%) manufactured by Seiko Chemical Co., Ltd. ; CX-260; average particle size 7μm)
5 parts were added, mixed and dispersed to prepare a stable dispersion. To this, 3 parts of a red pigment (manufactured by Dainippon Ink and Chemicals, Incorporated; DIRAC SL-3440) was added as a colorant and uniformly mixed to obtain a red paint formulation. This coating composition was applied and dried three times with a gravure coater (using a 110 mesh roll) on the surface of the artificial leather base created earlier, and then patterned with a heated embossing roll. An artificial leather having a coating film was obtained. The surface of the obtained artificial leather,
When touching the skin, it does not make you feel cold, feels warm, and has good feeling without sweatiness even on sweaty skin.It is excellent for volleyball, handball and basketball. Was. Table 1 shows the obtained characteristic values.

(Preparation of Coating Composition-2) Coating composition-2 was prepared with the following composition.

Crisbon NY320 100 parts (Dainippon Ink and Chemicals Co., Ltd.) Howlack A1004 White 80 parts (Dainippon Ink and Chemicals Co., Ltd.) Haurak A1008 Mat 30 parts (Dainippon Ink and Chemicals Ltd.) Isopropyl alcohol 50 Part Methyl ethyl ketone 40 parts N, N-dimethylformamide 10 parts (Preparation of coating composition 3) Coating composition 3 was prepared with the following composition.

LUCKSKIN-UA3295A 100 parts (manufactured by Seiko Chemical Co., Ltd.) (18%) Natural collagen particles CX-260 10 parts (manufactured by Showa Denko KK) Howlac B1356 Mat 20 parts (manufactured by Dainippon Ink & Chemicals, Inc.) N , N-Dimethylformamide 40 parts Methyl ethyl ketone 40 parts (Coating on artificial leather surface) Paint formulation liquid-2 was applied to the surface of the artificial leather base prepared in Example-1 using gravure roll (110 mesh) and dried. After repeating three times, a pattern is formed with a heated embossing roll, and a coating composition liquid-3 is further applied to the surface with a gravure roll (110 mesh) and dried three times.
An artificial leather having a white surface was obtained. The surface of the obtained artificial leather, when touching the skin, does not feel cold, feels warm, has no sticky feeling even on sweaty skin, and has excellent moisture permeability. And was suitable as a shoe upper material. The obtained characteristic values are also shown in Table 1.

(Preparation and application of coating compound liquid-4) Polyamino acid urethane (use of non-yellowing type urethane:
Mitsubishi Chemical Corporation PAU-300; Polyamino acid segment 3
5%) N, N-dimethylformamide solution (solid content 15%)
To 100 parts, 8 parts of particles made of natural collagen (manufactured by Showa Denko KK; CX-260; average particle size 7 μm) were added, mixed and dispersed to prepare a stable dispersion. Among them, black pigment (Dai Nippon Ink Chemical Industry Co., Ltd .;
8 parts of SL-3430) and 3 parts of a black dye (Kayaset BLACK-KR, Nippon Kayaku Co., Ltd.) were added and mixed uniformly to obtain a black paint. This black paint was applied on a patterned release paper so as to have a basis weight of 80 g / m ² , dried, and then applied with an adhesive. Then, the surface of the artificial leather base prepared in Example 1 was attached. And fully adhered. The surface of the artificial leather separated from the release paper, when touching the skin, does not feel cold, it feels warm, and even sweaty skin has no sticky feeling and has excellent tactile sensation, tennis It was suitable for racket grip materials and glove flats. Table 1 shows the obtained characteristic values.

Comparative Example 1 (Preparation of a coating composition liquid-5) A coating composition liquid-5 was prepared with the following composition.

Haurac A3454 (20%) 100 parts (Dainippon Ink and Chemicals, Inc.) Natural collagen particles CX-260 10 parts (Showa Denko KK) Haurac A1008 Mat 30 parts (Dainippon Ink and Chemicals, Inc.) 50 parts of isopropyl alcohol 50 parts of methyl ethyl ketone (application to artificial leather surface) Coating solution-2 is applied to the surface of the artificial leather base prepared in Example 1 with gravure roll (110 mesh) and dried three times. After the repetition, a pattern was formed with a heated embossing roll, and the coating composition liquid-5 was further applied to the surface with a gravure roll (110 mesh) and dried three times.
An artificial leather having a white surface was obtained. The transparency of the obtained artificial leather was unsatisfactory, and when a bending test was carried out, a powder which appeared to be particles CX-260 made of natural collagen dropped off. The obtained characteristic values are also shown in Table 1.

Comparative Example-2 (Preparation of coating composition -6) A coating composition -6 was prepared with the following composition.

LUCKSKIN-UA3295A 100 parts (manufactured by Seiko Chemical Co., Ltd.) (18%) Howlac B1356 Mat 20 parts (manufactured by Dainippon Ink and Chemicals, Inc.) N, N-dimethylformamide 40 parts Methyl ethyl ketone 40 parts (for artificial leather surface) Coating) After coating-drying the coating composition liquid-2 with a gravure roll (110 mesh) on the surface of the artificial leather base prepared in Example-1 three times, a pattern is formed with a heated embossing roll. The coating liquid-6 was coated on the surface with a gravure roll (110 mesh) and dried and dried three times.
An artificial leather having a white surface was obtained. The obtained artificial leather was unsatisfactory in transparency and had a slightly sticky surface feel. The obtained characteristic values are also shown in Table 1.

Comparative Example-3 (Preparation of coating composition liquid-7) A coating composition liquid-7 was prepared with the following composition.

Howlack A3454 (20%) 100 parts (Dainippon Ink and Chemicals, Inc.) Howlack A1008 Mat 30 parts (Dainippon Ink and Chemicals, Inc.) Isopropyl alcohol 50 parts Methyl ethyl ketone 50 parts (Coating on artificial leather surface) The coating composition liquid-2 was applied and dried three times on the surface of the artificial leather base prepared in Example 1 with a gravure roll (110 mesh), and then the pattern was formed with a heated embossing roll. The coating composition liquid-7 is applied to the gravure roll (110 mesh) and dried three times.
An artificial leather having a white surface was obtained. The obtained artificial leather is unsatisfactory in transparency, and the tactile feel of the surface is a sticky feeling peculiar to polyurethane of conventional artificial leather, especially when touching with sweaty skin, it feels sticky. there were. The obtained characteristic values are also shown in Table 1.

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Claims (3)

(57) [Claims] 1. A coating composition comprising a dispersion of particles of natural collagen dispersed in an organic solvent solution of a synthetic resin mainly composed of a polyamino acid urethane resin. 2. The polyamino acid urethane is a polyamino acid segment containing poly-γ-methyl-L-glutamate as a main component, and its content is 3% by weight to 85% by weight based on the weight of the polyamino acid urethane resin. Claim (1)
A paint formulation as described. 3. The coating composition according to claim 1, wherein the particles made of natural collagen are purified by biochemical treatment from animal skin or the like and crosslinked by heating.